Polyolefin and ceramic battery separator for non-aqueous battery applications

ABSTRACT

A ceramic microporous polyolefin battery separator membrane, high in air permeability, low in shrinkage and improved temperature resistance addresses the safety requirements of lithium ion batteries. The separators made by the current invention consists of one or more polyolefin polymers and kaolin fillers comprised of aluminum oxide and silicon oxide. The membranes of current invention have a thickness of 5-200 microns, air permeability of 1-200 sec/10 cc (Gurley seconds), and average pore diameter of less than 1 micron.

BACKGROUND OF THE INVENTION

Safety is a major concern when using lithium ion batteries (LIB) inhybrid electric vehicles (HEVs), pluggable HEVs and EVs. A separatorthat can improve the safety issues associated with LIBs and also meetsassembly and cell performance requirements as well as the cost criteriais needed for the HEV applications. This invention describes and claimssuch an improved separator.

Currently there are two types of secondary lithium ion batteries:

1. Those with cathode containing cobalt for high energy densitybatteries used in cell phones, notebook PCs and consumer electronics,which require a shutdown temperature activation of 130-150° C. and meltintegrity of more than 150° C.; and

2. Those with a non-cobalt cathode (mostly phosphate based) for highpower batteries, which do not require a shutdown temperature capability,but must have a separator with high temperature resistance.

Lithium-ion cells have two to three times higher energy density thannickel metal hydride batteries used in the current HEVs. Due to thishigh energy density of lithium ion batteries, automakers are eager toreplace the currently used nickel metal hydride battery packs in HEVswith a high power and high density lithium ion battery pack. Thus far,the safety issue (due to potential thermal run away of lithium ionbatteries) has been a major problem, preventing the use of lithium ionbatteries in the HEV applications. Among all of the commerciallyavailable polyolefin separators for LIB applications, none could passthe safety requirements for HEV applications. The only battery separatorthat is commercially available and has proven that it meets the safetyrequirements of HEVs is a ceramic separator called Seperion® fromDeggusa, the international chemical company headquartered in Dusseldorf,Germany. Seperion is produced by a non-woven polyethylene terephthalate(PET) precursor impregnated on both sides with ceramics containing nanoparticles of Al₂O₃ and SiO₂. Safety tests done by Deggusa, SandiaNational Labs and the US Army Research Labs have proven that indeedSeperion does improve the safety problems associated with LIBs. Zhang etal. reported:

“In nail penetration test on the 8 Ah Li-ion pouch cells, it was shownthat the maximum temperature of the cell using Separion separators wasonly 58° C. with a weight loss of 0.5% after nail penetration test,while that of the control cell using PE separators reached over 500° C.with a weight loss as high as 56.1%. Since the maximum temperature (58°C.) in the nail penetration test is far from the melting point of the PEmaterials, one may assume that the exceptional safety behavior of theSeparion separator is more related to the nano-size ceramic materials,instead of PET non-woven matrix.” S. S. Zhang, et al. “Journal of PowerSources 164 (2007) pp. 351-364.

However, due to a complicated phase inversion manufacturing process thathas been used in the production of the Separion separator, it has notbeen produced at a low cost, and therefore, it does not meet the costcriteria of lithium ion batteries in general and HEV/EVs in particular.In the current invention, in addition to offering comparable safetyfeatures, this invention replaces Al₂O₃ and SiO₂ with kaolin (a low costclay mineral filler consists of Al₂O₃ and SiO₂), and utilizes a low costprocess. The current invention does not require a nonwoven material andsubsequently conversion to a microporous membrane using an expensivephase inversion method. The wet process used in the current inventionhas proven track records; it is simple and has been used in theproduction of low cost lead acid PE separators for decades.

One aspect of the current invention provides a high performance low costceramic-like microporous separator high in air permeability of less than200 sec/10 cc, preferably less than 10 sec/10 cc, and with a shutdowntemperature between 130-150° C. This invention also provides a methodfor producing the same for consumer LIB applications.

Another aspect of the current invention provides a non-shutdownpolyolefin ceramic type microporous separator with high abuse tolerancebut with relatively low cost that meets both the safety and costrequirements of LIBs for EV/HEV applications.

The microporous membranes of current invention will have applications inair filtration, water purification (a filter for separatingmicroorganisms and viruses from water), size exclusion, sanitarynapkins, breathable closing and house wrap.

Inert fillers are also used in the production of battery separators,primarily for achieving better pore structures (added tortousity) andincreased porosity. However, fillers can also add properties such asstructural integrity (high puncture resistance), reduced shrinkage,improved thermal stability, and fire retardation. They also keep thebattery electrodes separated at high temperatures.

Examples of polymeric sheets with inert fillers include those describedin U.S. Pat. Nos. 3,351,495, 4,287,276, and U.S. Pat. Nos. 6,372,379 and6,949,315 (by current authors), in which, the electrolyte is capable ofpassing through the separator through microporous channels.

In U.S. Pat. No. 6,949,315 by the current inventors, TiO₂ filler is usedto improve the high temperature resistance of the separator. Addition ofTiO₂ to the formulation did indeed improve the thermal resistance of theseparator, however, TiO₂ is a heavy mineral (has a density of about 4.2gr/cm³) and is also very expensive and not particularly affordable to beused abundantly in commercially priced separators for lithium ionbatteries. Kaolin clay, in contrast, has lower density (density of 2.6gr/cm³), is very stable in the lithium ion battery environment and isrelatively inexpensive. In addition, kaolin clay has the capability toabsorb significantly more oil than TiO₂ (it creates more airpermeability) that leads to higher ionic conductivity of the separator.

Silica has also been used as a low-cost filler in battery separatorapplications for decades. However for use in lithium ion batteryapplications silica alone, without the presence of the aluminum oxide,may not improve the high temperature performance of the separator. Inaddition, due to silica filler's high moisture content, it may not besuitable for lithium ion batteries.

Kaolin clay is an abundant mineral and is a common constituent of theearth's crust. Clay occurs in many different forms, but kaolin or chinaclay is the purest and most versatile. Kaolin clays contain Al₂O₃ andSiO₂ with similar high heat resistance property as the ceramic materialused in the Separion separator, but cost significantly less. That is whyKaolin clays are commonly used in paints, paper, plastics, rubber, ink,pigments, fiber glass, cosmetics, cement and concrete, adhesive andsealants, cable and wire. They further have advantageous properties ofhardness, opacity, abrasion resistance, high brightness, and particlesize. They promote flattening and easy dispersion.

Calcined Kaolin, another inert filler appropriate for use in the presentinvention, is an anhydrous aluminum silicate produced by heatingultrafine natural kaolin to high temperatures in a kiln. The calcinationprocess increases whiteness and hardness, improves electricalproperties, and alters the size and shape of the kaolin particles.

Kaolin clay's nominal chemical properties are generally described asfollows: Silicon dioxide (wt%)=56.91, Iron oxide=0.93, Aluminumoxide=39.68, Titanium dioxide=0.54, Calcium oxide=0.16, Magnesiumoxide=0.16, Sodium oxide=0.60, and Potassium oxide=0.60

Clean kaolins are calcined by firing the powder in a rotary calciningkiln to a temperature high enough to effect loss of crystal water (andaccompanying mineral change). Calcined kaolin normally converts tomullite during this process. Based on where kaolin has been mined, theabove chemical properties could slightly vary in the composition oftheir trace elements.

For both shutdown and non-shutdown separators, the current inventionuses between 5% to 80% by weight kaolin, more preferably calcined kaolinas property enhancing filler (to achieve high heat resistance) in themicroporous membrane's formulations. In another version of thisinvention, kaolin clay can be replaced with materials consisting Al₂O₃and SiO₂. However, Al₂O₃ and SiO₂ may not be as economical as kaolin inthis application.

Different polyolefin polymers have been used in prior arts for makingbattery separators used in different applications, including lead acid,alkaline and lithium ion batteries. Polymers used in the currentinvention are selected from ultra high molecular weight polyethylene(UHMWPE with molecular weight more than 1 million) and polypropylene (PPwith a melt index of less than 2) or a mixture thereof as frame polymersand a high-density polyethylene (HDPE) having molecular weight between300,000 to 900,000 for achieving shutdown behavior between 130-150° C.For heat resistance separators (non-shutdown), the current inventionuses UHMWPE, with molecular weight more than 1 million, and PP or amixture thereof without HDPE.

The current invention basically utilizes a commonly used prior artmethod widely used for producing battery separators for lead acid,alkaline and lithium ion cells. This process starts by mixing andextruding polymers, filler (in this case, kaolin, calcined kaolin or amixture of Al₂O₃ and SiO₂), with a plasticizer (oil) at hightemperatures and pressure through a film die, casting the sheet, and wetstretching, either uni-axial or biaxial. Followed the wet stretching theoil is removed by solvent extraction and heat setting, creating amicroporous sheet. To achieve higher air permeability, the stretchingshould be done after the extraction step.

OBJECTS OF THE INVENTION

Against the foregoing background, it is a principal object of thepresent invention to provide microporous articles especially suitablefor use as battery separators and which possess improved properties withregard to their intended use in lithium ion cells.

It is another object of the present invention to provide suchmicroporous articles which possess improved air permeability, and whichare low in electrical impedance.

It is yet another object of the present invention to provide suchmicroporous articles which possess high thermal resistance.

It is yet another object of the present invention is to produce batteryseparators having improved safety features for use in lithium ion cells.

In yet another object of the present invention thermal runaway isavoided.

In yet another object of the present invention adequate shutdownbehavior is provided.

In yet another object of the present invention high thermal resistanceis provided.

It is yet another object of the present invention to provide an enhancedholding capacity and a uniform surface appearance when wound on awinding tube is provided for spiral wound separators.

It is yet another object of the present invention to provide an enhancedholding capacity and a uniform surface appearance when used inenveloping by an enveloping machine for prismatic cells, thereforeincreasing the electrolyte retention, wicking action and ease ofassembly.

It is yet another object of the present invention to provide batteryseparators that have lower material costs and can also be mass-producedat relatively low costs.

SUMMARY OF THE INVENTION

In accordance with one aspect of the current invention battery separatoris comprised of a mixture of kaolin clay and polyolefin.

In accordance with a second aspect of the invention, the batteryseparator has a thickness of 5 to 250 μm and air permeability of 1 to200 sec/10 cc.

In accordance with a third aspect of the invention the kaolin clayfurther comprises calcined kaolin.

In accordance with a fourth aspect of the invention the polyolefinfurther comprises an ulthira high molecular weight polyethylene (UHMWPE)having a minimum average molecular weight of 1×10⁶.

In accordance with a fifth aspect of the invention the polyolefin is amixture of UHMWPE having a minimum average molecular weight of 1×10⁶ anda polypropylene (PP) having a melt index of 2 or less, and wherein theweight ratio of UHMWPE to PP is 50% or more.

In accordance with a sixth aspect of the invention the weight percentageratio of the kaolin clay in the mix is between 20 to 80%, and whereinthe separator is not subject to shutdown, regardless of temperature.

In accordance with a seventh aspect of the invention the microporousmembrane has a melt integrity of 150° C. or higher.

In accordance with an eighth aspect of the invention the polyolefincomprises a mixture of 10% to 50% by weight of UHMWPE having minimumaverage molecular weight of 1×10^(6,) and 40% to 70% by weight of a highdensity polyethylene having an average molecular weight between 300,000to 800,000.

In accordance with a ninth aspect of the invention the weight percent ofcalcined kaolin in the mixture is between 5% and 20%.

In accordance with a tenth aspect of the invention the battery separatorhas shutdown activation between 130° C. and 150° C.

In accordance with an eleventh aspect of the invention the meltintegrity of the battery separator is 150° C. or higher.

In accordance with a twelfth aspect of the invention the batteryseparator is comprised of between 20% and 80% by weight of syntheticAl₂O₃ and between 20% and 80% by weight of SiO₂, and polyolefin, thebattery separator having a thickness of 5 to 250 μm and an airpermeability of 1 to 200 sec/10 cc.

DETAILED DESCRIPTION OF THE INVENTION

A microporous battery separator made by wet process comprised ofpolyolefin and kaolin filler. Kaolin, a mineral consisting of Al₂O₃ andSiO₂, is found extensively in Kaolin clay. More preferably calcinedkaolin may be used. The polyolefin can be selected from ultra highmolecular weight polyethylene (UHMWPE) having an average molecularweight of 1×10⁶ or higher, polypropylene with melt index of less than 2and high-density polyethylene with average molecular weight of300,000-900,000 and the mixture thereof.

The wet process starts by mixing and extruding a polymer and filler, inthis case kaolin, with a plasticizer (oil) through a sheet die,calendaring/casting the sheet, followed by solvent extraction and thendry stretching/heat setting. Due to high oil absorbency of kaolin themicroporous membranes produced with this method will have very high airpermeability (low Gurley number). The presence of kaolin in theseparator of the current invention will contribute to its high heatresistance properties and will stop thermal runaway in LIB cells.

The process by which the proposed separators are made is broadlycomprised of making a microporous membrane by forming a homogeneousadmixture of one or more polyolefin polymers, including a suitableplastisizer (oil) for the polyolefin and including a particulate filler,as described herein below.

The specific methods for making these membrane sheets are well known inprior art. By way of non-limiting examples, the following references usethe similar wet technology, U.S. Pat. Nos. 3,351,495; 4,287,276 andthose from the same inventors, U.S. Pat. No. 6,372,379 and 6,949,315.

Regarding the preferred method for making the membrane with high heatresistance, the components of the admixture are: an ultra high molecularweight polyethylene (UHMWPE) having an average molecular weight of 1×10⁶or more and a kaolin or calcined kaolin.

Alternatively a mixture of ultra high molecular weight polyethylenehaving an average molecular weight of 1×10⁶ and PP with melt index ofless than 2 with same fillers are used.

For making a membrane with shutdown behavior, the formulation willconsist of a UHMWPE having an average molecular weight of 1×10⁶ or moreas a frame polymer, and a shutdown polyethylene having an averagemolecular weight between 300,000 to 900,000 and kaolin or calcinedkaolin (or a mixture of Al₂O₃ and SiO₂) filler.

Dry blend composition for high temperature resistance and no shutdown isbased on required properties such as tensile and puncture strength.Therefore, the amount of calcined kaolin in the separator formulationcould be between 20 and 80 percent by weight. More preferably, thisamount should be between 30 and 50 percent by weight. For a shutdownseparator, the amount of calcined kaolin should be less than 20 percentby weight in the dry blend. More preferably this amount should bebetween 5 and 15 percent by weight.

The present invention also provides a method for producing microporouspolyolefin membranes which are comprised of some general steps of (a)preparing the above dry blend and (b) extruding the dry blend with from30 to percent by weight of suitable plasticizer, typically oil, througha film die, and (c) casting/calendering the gel-like extrudate (d)removing the plasticizer using a solvent extraction method (e) based onthe formulation, stretching and heat setting the extracted material inboth directions at 115 to 140 degrees C.

Other minor additives such as carbon black, most commonly used in priorart for different reasons such as increasing the surface area or generalappearance, can also be incorporated in the formulation. Carbon blackpellets made from a mixture of carbon black and high density or lowdensity polyethylene are generally commercially available.

In accordance with the prior art, conventional stabilizers orantioxidants may be employed in the compositions of the presentinvention to prevent thermal and oxidative degradation of the polyolefincomponent. Representatives of the stabilizers are 4,4 thiobis(6-tert-butyl-m-cresol) (“Santonox”), and2,6-di-tert-butyl-4-methylphenol (“Ionol”).

The microporous sheet material made by this method should be a film thatis less than 250 microns and preferably less than 25 microns inthickness. The air permeability of the microporous membrane of thepresent invention is between 1 to 200 Gurley seconds (sec/10 cc),preferably between 1 to 50 Gurley seconds and, and a heat resistance ofmore than 150° C., preferably between 165 to 200° C.

The following test methods were used for measurements:

(1) Thickness—Thickness (mil or micron)—is determined using a precisionmicrometer.

(2) Air permeability—measured by using a Gurley densometer (Model 4120),ASTM-D726(B)—Gurley is the time in seconds required to pass 10 cc of airthrough one square inch of product under a pressure of 12.2 inches ofwater.

(3) Shutdown—measured using the method described by Spotnitz, et al. R.Spotnitz,, et al. “Shutdown Battery Separators”, The 12^(th) Intl. Sem.Primary & Secondary Battery Technology and Applications, 1995.

(4) Melt integrity—measured using thermal mechanical analysis (TMA), itis a the temperature that a strip of 1 mil thick membrane (1″ width and6″ length) can no longer hold a 5 gram weight

(5) Shrinkage—measured in both directions after 60 min at 90° C.

(6) Tensile strength—calculated in machine direction by measuringpercent offset at 1000 psi

(7) Puncture resistance—measured by pressing a cylindrical pin (2 mmdiameter) with a hemispherical tip through a sample. The maximum loadoccurring is a measure of the puncture resistance.

The invention will be explained in more detail by reference to thefollowing Examples, but the invention should not be construed as beinglimited by these Examples in any way.

This invention primarily based on using kaolin or Calcined kaolin with apolyolefin to construct mircroporous membranes, however, kaolin can bereplaced by its main constituent metal oxides, a mixture of Al₂O₃ andSiO₂ (20 to 80 percentage by weight Al₂O₃ and 20 to 80 percentage byweight of SiO₂). The kaolin, particularly in the form of kaolin clay, isclearly more cost competitive than the other forms of this chemicalcompound.

EXAMPLE 1

A dry-blend consisting of 50% by weight of a UHMW polyethylene having Mwof 1×10⁶, 50% by weight of kaolin with density of 2.6 was prepared. Themixture was fed into an extruder. The dry blend mixture was melt-kneadedin the extruder while feeding 60% by weight of liquid paraffin making asolution.

The above solution was extruded from a film die into the form of asheet. Using a two-roll casting roll, the gel sheet was subsequentlycooled down producing a 2 to 4 mil thick gel sheet. The liquid paraffinin the gel sheet was extracted by solvent and dried. The driedmicroporous sheet was subsequently stretched in both directions at 125°C. for 100% and also heat set at 120° C., producing a 25 microns thickmicroporous membrane.

The sample produced above was tested for air permeability (Gurleynumber), shutdown and melt integrity, shrinkage, tensile strength, andpuncture resistance. The Gurley number was less than 10 seconds, thesample did not shut down, had a melt integrity more than 190° C.,shrinkage of less than 5%, tensile strength of less than 2% offset, andpuncture resistance of more than 400 grams. The Gurley number prior tostretching of 2-4 mil (50-200 microns) thick material was measured andit was less than 200 seconds.

EXAMPLE 2

Except by replacing kaolin with calcined kaolin, the same formulationand procedures of Example 1 were repeated to obtain a microporousmembrane.

We noticed that the oil dispersion of calcined kaolin is better thankaolin. The sample produced above was tested for air permeability(Gurley number), shutdown and melt integrity, shrinkage, tensilestrength, and puncture resistance. The Gurley number was less than 10seconds, the sample did not shutdown, had a melt integrity more than190° C., shrinkage of less than 5%, tensile strength of less than 2%offset, puncture resistance of more than 450 grams. The Gurley numberprior to stretching of 2-4 mil (50-200 microns) thick material wasmeasured and it was less than 200 seconds.

EXAMPLE 3

Except for using a dry blend mixture of 40% by weight of a UHMWpolyethylene having Mw of 1×10⁶, 10% by weight of a UHMW polyethylenehaving Mw of 3×10⁶ and 50% by weight calcined kaolin, the sameprocedures of Example 1 were repeated to obtain a microporous membrane.

The sample produced above was tested for air permeability (Gurleynumber), shutdown and melt integrity, shrinkage, tensile strength, andpuncture resistance. The Gurley number was less than 10 seconds, thesample did not shutdown, had a melt integrity more than 190° C.,shrinkage of less than 5%, tensile strength of less than 2% offset,puncture resistance of more than 480 grams. The Gurley number prior tostretching of 2-4 mil (50-200 microns) thick material was measured andit was less than 200 seconds.

EXAMPLE 4

Except for using a dry blend mixture of 20% by weight of a UHMWpolyethylene having Mw of 1×10⁶, and 80% by weight calcined kaolin, thesame procedures of Example 1 were repeated to obtain a microporousmembrane.

The sample produced above was tested for air permeability (Gurleynumber), shutdown and melt integrity, shrinkage, tensile strength, andpuncture resistance. The Gurley number was less than 10 seconds, thesample did not shutdown, had a melt integrity more than 190° C.,shrinkage of less than 5%, tensile strength of less than 2% offset,puncture resistance of more than 200 grams. The Gurley number prior tostretching of 2-4 mil (50-200 microns) thick material was measured andit was less than 200 seconds.

EXAMPLE 5

Except for using a dry blend mixture of 80% by weight of a UHMWpolyethylene having Mw of 1×10⁶, and 20% by weight calcined kaolin, thesame procedures of Example 1 were repeated to obtain a microporousmembrane.

The sample produced above was tested for air permeability (Gurleynumber), shutdown and melt integrity, shrinkage, tensile strength, andpuncture resistance. The Gurley number was less than 10 seconds, thesample did not shutdown, had a melt integrity more than 190° C.,shrinkage of less than 5%, tensile strength of less than 2% offset,puncture resistance of more than 800 grams. The Gurley number prior tostretching of 2-4 mil (50-200 microns) thick material was measured andit was less than 200 seconds.

EXAMPLE 6

Except for using a dry blend mixture of 40% by weight of a UHMWpolyethylene having Mw of 1×10⁶, 20% PP with melt index of less than 2and 40% by weight calcined kaolin, the same procedures of Example 1 wererepeated with a different process conditions. The dried microporoussheet was subsequently stretched in both directions at 140° C. for 100%and also heat set at 135° C., producing a 25 microns thick microporousmembrane.

The sample produced above was tested for air permeability (Gurleynumber), shutdown and melt integrity, shrinkage, tensile strength, andpuncture resistance. The Gurley number was less than 10 seconds, thesample did not shutdown, had a melt integrity more than 190° C.,shrinkage of less than 5%, tensile strength of less than 2% offset,puncture resistance of more than 550 grams. The Gurley number prior tostretching of 2-4 mil (50-200 microns) thick material was measured andit was less than 200 seconds.

EXAMPLE 7

Except for using a dry blend mixture of 50% by weight of a UHMWpolyethylene having Mw of 3×10⁶, and 50% by weight calcined kaolin, thesame procedures of Example 1 were repeated.

The sample produced above was tested for air permeability (Gurleynumber), shutdown and melt integrity, shrinkage, tensile strength, andpuncture resistance. The Gurley number was less than 10 seconds, thesample did not shutdown, had a melt integrity more than 190° C.,shrinkage of less than 5%, tensile strength of less than 2% offset,puncture resistance of more than 500 grams. The Gurley number prior tostretching of 2-4 mil (50-200 microns) thick material was measured andit was less than 200 seconds.

EXAMPLE 8

Except for using a dry blend mixture of 50% by weight of a UHMWpolyethylene having Mw of 5×10⁶, and 50% by weight calcined kaolin, thesame procedures of Example 1 were repeated.

The sample produced above was tested for air permeability (Gurleynumber), shutdown and melt integrity, shrinkage, tensile strength, andpuncture resistance. The Gurley number was less than 10 seconds, thesample did not shutdown, had a melt integrity more than 190° C.,shrinkage of less than 5%, tensile strength of less than 2% offset,puncture resistance of more than 600 grams. The Gurley number prior tostretching of 2-4 mil (50-200 microns) thick material was measured andit was less than 200 seconds.

EXAMPLE 9

Except for using a dry blend mixture of 50% by weight of a UHMWpolyethylene having Mw of 5×10⁶, 40% by weight of a UHMW polyethylenehaving Mw of about 800,000 and 10% by weight calcined kaolin, the sameprocedures of Example 1 were repeated.

The sample produced above was tested for air permeability (Gurleynumber), shutdown and melt integrity, shrinkage, tensile strength, andpuncture resistance. The Gurley number was less than 10 seconds, thesample shutdown at 146° C., had a melt integrity more than 190° C.,shrinkage of less than 5%, tensile strength of less than 2% offset,puncture resistance of more than 550 grams. The Gurley number prior tostretching of 2-4 mil (50-200 microns) thick material was measured andit was less than 200 seconds.

EXAMPLE 10

Except for using a dry blend mixture of 40% by weight of a UHMWpolyethylene having Mw of 5×10⁶, 40% by weight of a UHMW polyethylenehaving Mw of about 300,000 and 20% by weight calcined kaolin, the sameprocedures of Example 1 were repeated.

The sample produced above was tested for air permeability (Gurleynumber), shutdown and melt integrity, shrinkage, tensile strength, andpuncture resistance. The Gurley number was less than 10 seconds, thesample shutdown at 135° C., had a melt integrity more than 190° C.,shrinkage of less than 5%, tensile strength of less than 2% offset,puncture resistance of more than 500 grams. The Gurley number prior tostretching of 2-4 mil (50-200 microns) thick material was measured andit was less than 200 seconds.

EXAMPLE 11

Except for using a dry blend mixture of 25% by weight of a UHMWpolyethylene having Mw of 5×10⁶, 70% by weight of a UHMW polyethylenehaving Mw of about 300,000 and 5% by weight calcined kaolin, the sameprocedures of Example 1 were repeated.

The sample produced above was tested for air permeability (Gurleynumber), shutdown and melt integrity, shrinkage, tensile strength, andpuncture resistance. The Gurley number was less than 10 seconds, thesample shutdown at 131° C., had a melt integrity more than 190° C.,shrinkage of less than 5%, tensile strength of less than 2% offset,puncture resistance of more than 500 grams. The Gurley number prior tostretching of 2-4 mil (50-200 microns) thick material was measured andit was less than 200 seconds.

These examples are summarized in the table appearing below.

Examples 1 2 3 4 5 6 7 8 9 10 11 Formulation UHMWPE Mwt >1 million 50%50% 40% 20% 80% 40% UHMWPE Mwt >3 million 10% 50% 25% UHMWPE Mwt >5million 50% 50% 40% Polypropylene 20% HDPE Mwt 800 40% HDPE Mwt 300 40%70% Kaolin 50% Calcined Kaolin 50% 50% 80% 20% 40% 50% 50% 10% 20%  5%Properties Thickness (microns) 25 25 25 25 25 25 25 25 25 25 25 Gurley(sec) <10 <10 <10 <10 <10 <10 <10 <10 <10 <10 <10 Shrinkage MD % <5 <5<5 <5 <5 <5 <5 <5 <5 <5 <5 Shrinkage TD % <5 <5 <5 <5 <5 <5 <5 <5 <5 <5<5 Shutdown Deg. C. None None None None None None None None 148 135 131Melt Integrity Deg.C. >190 >190 >190 >190 >190 >190 >190 >190 >190 >190 >190 Puncturegrams >400 >450 >480 >200 >800 >550 >500 >600 >550 >500 >500 Tensile %offset at 1000 psi <2% <2% <2% <2% <2% <2% <2% <2% <2% <2% <2%

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof. To cite only one of manypossible examples, the ultra high molecular weight polyethylene can bereplaced with a high-density polyethylene or a mixture of two or threeultra high molecular weight polyethylene and high-density polyethyleneor other polyolefins, polyolefin copolymers or derivatives thereof andthe kaolin filler or the mixture of Al₂O₃ and SiO₂ can be replaced byother suitable and property enhancing stable fillers.

1-14. (canceled)
 15. A separator for a lithium-ion battery withresistance to thermal runaway and without shutdown, the separatorcomprising a combination of polyolefin and kaolin, wherein thecombination is formed into a microporous membrane having no shutdowntemperature.
 16. The separator of claim 15 wherein the kaolin is acalcined kaolin.
 17. The separator of claim 15 wherein the polyolefinincludes an ultra high molecular weight polyethylene having an averagemolecular weight of 1×10⁶ or more.
 18. The separator of claim 17 whereinthe polyolefin includes polypropylene with a melt index of 2 or less.19. The separator of claim 15 wherein the polyolefin includes an ultrahigh molecular weight polyethylene having an average molecular weight of1×10⁶ or more and polypropylene with a melt index of 2 or less and thekaolin is a calcined kaolin.
 20. The separator of claim 19 wherein aweight ratio of the ultra high molecular weight polyethylene to thepolypropylene is about two to one.
 21. The separator of claim 19 whereina weight ratio of polyolefin to calcined kaolin is about three to two.22. The separator of claim 15 wherein the microporous membrane has aporosity of at least 60% and an air permeability of between 1 and 200sec/10 cc.
 23. The separator of claim 15 wherein the separator has amelt integrity of at least 190° C., a puncture resistance of more than550 grams and a tensile strength at 1000 psi of less than 2% offset. 24.A lithium-ion battery with resistance to thermal runaway and withoutshutdown, the battery comprising a separator formed of a combination ofpolyolefin and kaolin, wherein the combination is formed into amicroporous membrane having no shutdown temperature.
 25. The battery ofclaim 24 wherein the kaolin is a calcined kaolin.
 26. The battery ofclaim 24 wherein the polyolefin includes an ultra high molecular weightpolyethylene having an average molecular weight of 1×10⁶ or more. 27.The battery of claim 26 wherein the polyolefin includes polypropylenewith a melt index of 2 or less.
 28. The battery of claim 24 wherein thepolyolefin includes an ultra high molecular weight polyethylene havingan average molecular weight of 1×10⁶ or more and polypropylene with amelt index of 2 or less and the kaolin is a calcined kaolin.
 29. Thebattery of claim 28 wherein a weight ratio of the ultra high molecularweight polyethylene to the polypropylene is about two to one.
 30. Thebattery of claim 28 wherein a weight ratio of polyolefin to calcinedkaolin is about three to two.
 31. The battery of claim 24 wherein themicroporous membrane has a porosity of at least 60% and an airpermeability of between 1 and 200 sec/10 cc.
 32. The battery of claim 24wherein the separator has a melt integrity of at least 190° C., apuncture resistance of more than 550 grams and a tensile strength at1000 psi of less than 2% offset.